A 2‐fold Interpenetrated Framework based on Tetranuclear Heterometallic Cluster: Synthesis,Structure and Magnetic Properties

A 2‐fold parallel interpenetrated polymer, ZnCo(OH)(pheno)(p‐BDC)_1.5·H₂O ( 1 ) (pheno = phenanthrene‐9,10‐dione; p‐BDC = 1,4‐benzenedicarboxylate) has been prepared by hydrothermal synthesis and structurally characterized by IR, elemental analysis, ICP and single crystal X‐ray diffraction. Complex 1 crystallizes in the orthorhombic space group Pbca and affords a three‐dimensional (3D) six‐connected α‐Po network. The magnetic behavior for 1 was studied in the temperature range of 1.8‐300 K.     

Synthese,Strukturen und X‐/Q‐Band‐EPR‐Untersuchungen von N,N‐Diethyl‐N′‐3,5‐di(trifluormethyl)benzoylthioureato‐Komplexen des CuII,NiII und PdII sowie EPR‐spektroskopische Charakterisierung eines CuII‐CuII‐Dimers

The synthesis and the structures of (i) the ligand N,N‐Diethyl‐N′‐3,5‐di(trifluoromethyl)benzoylthiourea HEt₂dtfmbtu and (ii) the Ni^II and Pd^II complexes of HEt₂dtfmbtu are reported. The ligand coordinates bidendate forming bis chelates. The Ni^II and the Pd^II complexes are isostructural. The also prepared Cu^II complex could not be characterized by X‐ray analysis. However, the preparation of diamagnetically diluted powders Cu/Ni(Et₂dtfmbtu)₂ and Cu/Pd(Et₂dtfmbtu)₂ suitable for EPR studies was successful. The EPR spectra of the Cu/Ni and Cu/Pd systems show noticeable differences for the symmetry of the CuS₂O₂ unit in both complexes: the Cu/Pd system is characterized by axially‐symmetric g< and A ^cu tensors; for the Cu/Ni system g and A ^Cu have rhombic symmetry. EPR studies on frozen solutions of the Cu^II complex show the presence of a Cu^II‐Cu^II dimer which is the first observed for Cu^II acylthioureato complexes up to now. The parameters of the fine structure tensor were used for the estimation of the Cu^II‐Cu^II distance.     

Divalent Metal 2,5‐Thiophenedicarboxylate Coordination Polymers with the Conformationally Flexible Bis(4‐pyridyl­formyl)homopiperazine Ligand

Divalent metal coordination polymers containing the rigid 2,5‐thiophenedicarboxylate (tdc) ligand and the conformationally flexible dipyridylamide ligand bis(4‐pyridylformyl)homopiperazine (bpfh) show different layer topologies and chirality. As determined by single‐crystal X‐ray diffraction, {[Cd(tdc)(bpfh)(H₂O)] · 3H₂O}_n ( 1 ) shows a twofold parallel interpenetrated centrosymmetric (4,4) layered grid structure. {[Zn(tdc)(bpfh)] · H₂O}_n ( 2 ) exhibits a similar system of twofold interpenetrated (4,4) grid‐like layers, but in contrast to 1 , it crystallizes in an acentric space group. {[Ni₂(tdc)₂(bpfh)₂(H₂O)] · 2H₂O}_n ( 3 ) possesses {Ni₂(μ‐H₂O)(OCO)₂} dimeric units connected into a doubled layer motif by the full span of the tdc and bpfh ligands. Weak antiferromagnetic coupling is observed within the dimeric units in 3 [g = 2.172(6) and J = –0.79(1) cm^–1]. Compounds 1 and 2 undergo blue‐violet fluorescence upon ultraviolet irradiation; the cadmium derivative 1 shows potential as a sensor for the solution‐phase detection of nitrobenzene although coordination polymer exfoliation likely occurs. Thermal decomposition behavior of the three new phases is also discussed.     

Synthesis,Structure and Luminescence of Cd3Cu2 and Cd2Ni4 Heteronuclear Complexes with Macrocyclic Oxamide and 5‐Sulfosalicylicate

Two novel heteronuclear complexes [Cd₃(SSAL)₂(CuL)₂(H₂O)₄]_n ( 1 ) and [Cd₂(HSSAL)₂(NiL)₄] · 4H₂O ( 2 ) were synthesized and structurally determined, where SSAL is the fully deprotonated 5‐sulfosalicylic ion (CuL and NiL, H₂L = 2,3‐dioxo‐5,6,14,15‐dibenzo‐1,4,8,12‐tetraazacyclopentadeca‐7,13‐diene). Compound 1 displays a 1D ladder‐like chain and all these chains are further interlinked through hydrogen bonds resulting in a 2D architecture. The structure of 2 consists of 5‐sulfosalicylates and an oxamido‐bridge and is arranged in butterfly‐like hexanuclear molecules. The luminescent properties of compounds 1 and 2 are also discussed.     

Synthesis and Crystal Structure of Two CuII‐benzene‐1,2,4,5‐tetracarboxylates with Three‐Dimensional Open Frameworks

Two new three‐dimensional frameworks with zeolite‐like channels were prepared in the presence of 1,6‐diaminohexane. Cu_1.5(H₃N–(CH₂)₆–NH₃)_0.5[C₆H₂(COO)₄] · 5H₂O ( 1 ) crystallizes in the triclinic space group P$\bar{1}$ with a = 772.56(7), b = 1110.36(7), c = 1111.98(8) pm, α = 98.720(7)°, β = 108.246(9)°, and γ = 95.559(7)°. Cu₂(H₃N–(CH₂)₆–NH₃)_0.5(OH)[C₆H₂(COO)₄] · 3H₂O ( 2 ) crystallizes in the monoclinic space group P2/c with a = 1159.34(11), b = 1059.44(7), c = 1582.2(2) pm, and β = 106.130(11)°. The Cu²⁺ coordination polyhedra are connected by [C₆H₂(COO)₄]^4– anions to yield three‐dimensional frameworks with wide centrosymmetric channel‐like voids. Complex 1 reveals voids extending along [100] with diagonals of 900 pm and 300 pm, whereas in complex 2 the diagonal of the nearly rectangular crossection of the channels extending parallel to [001] is 900 pm. The negative excess charges of the frameworks are compensated by [H₃N–(CH₂)₆–NH₃]²⁺ cations, which occupy the voids along with water molecules. The [H₃N–(CH₂)₆–NH₃]²⁺ cations are not connected to Cu²⁺ and have served as templates.     

Three Dicyanidometallate(I)‐based Complexes Incorporating Hydrogen‐bonding, π–π Packing and d10–d10 Interactions with Auxiliary 2,2′‐Bipyridyl‐like Ligands

To investigate the influence of the non‐covalent interactions, such as hydrogen‐bonding, π–π packing and d¹⁰–d¹⁰ interactions in the supramolecular motifs, three cyanido‐bridged heterobimetallic discrete complexes {Mn(bipy)₂(H₂O)[Ag(CN)₂]}[Ag(CN)₂] ( 1 ), {Mn(phen)₂(H₂O)[Au(CN)₂]}₂[Au(CN)₂]₂ · 4H₂O ( 2 ), and {Cd(bipy)₂(H₂O)[Au(CN)₂]}[Au(CN)₂] ( 3 ) (bipy = 2,2′‐bipyridine, and phen = 1,10‐phenanthroline), which are based on dicyanidometallate(I) groups with 1:2 stoichiometry of metal ions and 2,2′‐bipyridyl‐like co‐ligands were synthesized and structurally characterized. In compound 1 , hydrogen bonding and π–π interactions governed the supramolecular contacts. In compound 2 , the incorporation of aurophilic, hydrogen bonding and π–π interactions result in a 3D supramolecular network. In compound 3 , hydrogen bonding and π–π stacking interactions result in a 2D supramolecular layer. In the three complexes, hydrogen‐bonding, π–π packing and/or d¹⁰–d¹⁰ interactions can play important roles in increasing the dimensionality of supramolecular assemblies.     

A Redox‐Active 2D Metal–Organic Framework for Efficient Lithium Storage with Extraordinary High Capacity

Metal–organic framework cathodes usually exhibit low capacity and poor electrochemical performance for Li‐ion storage owing to intrinsic low conductivity and inferior redox activity. Now a redox‐active 2D copper–benzoquinoid (Cu‐THQ) MOF has been synthesized by a simple solvothermal method. The abundant porosity and intrinsic redox character endow the 2D Cu‐THQ MOF with promising electrochemical activity. Superior performance is achieved as a Li‐ion battery cathode with a high reversible capacity (387 mA h g^?1), large specific energy density (775 Wh kg^?1), and good cycling stability. The reaction mechanism is unveiled by comprehensive spectroscopic techniques: a three‐electron redox reaction per coordination unit and one‐electron redox reaction per copper ion mechanism is demonstrated. This elucidatory understanding sheds new light on future rational design of high‐performance MOF‐based cathode materials for efficient energy storage and conversion.     

Sorption Behavior and Magnetic Properties of A Heterometallic Organic Framework with Octahedral Cages and One‐Dimensional Channels

The Zn^II‐Co^II organic framework [Me₂NH₂][Zn₂Co(μ₃‐OH)(BTC)₂(H₂O)] · 2H₂O ( FJI‐6 ) (H₃BTC = 1, 3,5‐benzenetricarboxylic acid and DMA = N.N′‐dimethyl acetamide), was synthesized and structurally characterized. FJI‐6 shows a three‐dimensional heterometallic microporous framework with coexisting octahedral cages and one‐dimensional channels assembled by Zn₂Co(μ₃‐OH)(CO₂)₆ secondary building units. In addition, the sorption behavior and magnetic properties of FJI‐6 were investigated.     

Two 3d‐4f Heterometallic Coordination Polymers of Macrocyclic Oxamide with Benzotriazole‐5‐carboxylate Co‐ligand: Syntheses,Crystal Structures and Magnetic Properties

Two heterometallic 3d–4f coordination polymers, [Gd(CuL)₂(Hbtca)(btca)(H₂O)] · 2H₂O ( 1 ) and [Er(CuL)₂(Hbtca)(btca)(H₂O)] · H₂O · CH₃OH ( 2 ) (CuL, H₂L = 2,3‐dioxo‐5,6,14,15‐dibenzo‐1,4,8,12‐tetraazacyclo‐pentadeca‐7,13‐dien; H₂btca = benzotriazole‐5‐carboxylic acid) were synthesized by solvothermal methods and characterized by single‐crystal X‐ray diffraction. Complexes 1 and 2 exhibit a double‐strand meso‐helical chain structures formed by [Ln^IIICu^II₂] (Ln^III = Gd, Er) units by oxamide and benzotriazole‐5‐carboxylate bridges. They are isomorphic except that one free water molecule of 1 is replaced by a methanol molecule. All 1D chains are further interlinked by hydrogen bonds resulting in a 3D supramolecular architecture. The magnetic properties of the compound 1 and 2 are also discussed.     

Copper(II) Complexes with Asymmetrical Schiff Base Ligands Derived from 2‐Acetylpyrazine

New copper(II) complexes of asymmetrical tetradentate Schiff bases containing pyrazine have been prepared and thoroughly characterised by elemental analysis, IR and electronic spectroscopy, mass spectrometry and magnetic measurements. Two alternative methods were used in the isolation of the complexes: template synthesis in the preparation of Cu(SalDpyz)ClO₄ (HSalDPyz = derived from the condensation of salicylaldehyde, acetylpyrazine and 1,2‐ethylendiamine, 2‐methyl‐1,2‐propylendiamine, 1,2‐phenylendiamine) and direct interaction between copper perchlorate and the corresponding Schiff base, as in the isolation of Cu(AEPyz)(ClO₄) (HAEPyz = (Z)‐4‐[2‐{[2‐{[(E)‐1‐(pyrazinyl)ethylidene]amino} ethyl)amino]‐3‐penten‐2‐one)]. [Cu(SalEn)(py)(OClO₃)][Cu(SalEn)(py)]ClO₄ ( 1 ) (SalEn = 4‐(2‐hydroxyphenyl)‐3‐aza‐3‐buten‐1‐amino, py = pyridine), metal precursor in the preparation of Cu(SalEnpyz)(ClO₄) (HSalEnpyz = 2‐{E(2‐{[(E)‐1‐(2‐pyrazinyl)ethylidene]amino}ethyl)imino]methyl}phenol), was crystallographically characterised. The crystal structure of [Cu(AEpyz)]ClO₄ ( 2 ) is also reported.     

A Polyhedron‐based Metal‐Organic Framework showing high CO2 Adsorption Capacity

A novel porous copper‐based metal‐organic framework {[Cu₂(TTDA)₂]*(DMA)₇}_n ( 1 ) (DMA = N,N‐dimethylacetamide) was designed and synthesized via the combination of a dual‐functional organic linker 5′‐(4‐(4H‐1,2,4‐triazol‐4‐yl)phenyl)‐[1,1′:3′,1′′‐terphenyl]‐4,4′′‐dicarboxylic acid (H₂TTDA) and a dinuclear Cu^II paddle‐wheel cluster. This MOF is characterized by elemental analysis, powder X‐ray diffraction (PXRD), thermo gravimetric analysis (TGA), and single‐crystal X‐ray diffraction. The framework is constructed from two types of cages (octahedral and cuboctahedral cages) and exhibits two types of circular‐shaped channels of approximate size of 5.8 and 11.4 Å along the crystallographic c axis. The gas sorption experiments indicate that it possesses a large surface area (1687 m² · g^–1) and high CO₂ adsorption capacities around room temperature (up to 172 cm³ · g^–1 at 273 K and 124 cm³ · g^–1 at 298 K).     

Solvent‐Dependent Synthesis from Layer to Microporous Pillared‐Layer Framework for Selective Sorption of Gas Light Hydrocarbons

Three metal‐organic frameworks, [Zn₃(bdc)₃(DMA)₂] ( 1 ) (H₂bdc = terephthalic acid; DMA = N,N‐dimethylacetamide), [Zn₃(bdc)₃(DMA)(DMPU)] ( 2 ) (DMPU = 1,3‐dimethylpropyleneurea), and [Zn₃(bdc)₄(Hdma)₂] ( 3 ) [Hdma = protonated dimethylamine (Me₂NH₂)] were synthesized by using different solvents. The solvents determine the framework architectures range from layer to microporous pillared‐layer framework. The microporous framework has 8‐connected bcg topology and shows selective sorption ability for gas light hydrocarbons.     

Polynuclear Chlorido Metal(II) Complexes with 1,2‐Di(1H‐­tetrazol‐1‐yl)ethane as Ligand Forming One‐ and Two‐dimensional Structures

The preparation and characterization of three metal(II) chlorido complexes with 1,2‐di(1H‐tetrazol‐1‐yl)ethane (dte) ( 1 ) as ligand is presented. The complexes have the following formula: [CoCl₂(μ‐dte)(dte)₂]_n ( 2 ), [CuCl₂(μ‐dte)₂]_n ( 3 ), and [Cd(μ‐Cl)₂(μ‐dte)]_n ( 4 ). Single crystal X‐ray diffraction of all three metal complexes was performed and the structures are discussed. All three central metal atoms are connected to polynuclear structures by the μ‐bridging ligand. Cobalt and copper are connected to one‐dimensional chains. The central cadmium(II) atoms are additionally connected by the chloride anions to a two‐dimensional network. Further, the cobalt(II) complex represents a special case with two terminal dte ligands.     

Heterometallic Polynuclear Complexes of Macrocyclic ­Oxamide with Pyrazine‐2, 3‐dicarboxylic Acid: Synthesis,Crystal Structure,and Magnetic Properties

Three novel complexes, namely [Zn(CuL)(pzdc)]₂ · 5H₂O ( 1 ), [Zn(NiL)(pzdc)]₂ · 5H₂O ( 2 ), and [Gd₂(pzdc)₂(NiL)₆](ClO₄)₂ · 6H₂O ( 3 ) (CuL and NiL, H₂L = 2, 3‐dioxo‐5, 6, 14, 15‐dibenzo‐1, 4, 8, 12‐tetraazacyclo‐pentadeca‐7, 13‐dien and H₂pzdc = pyrazine‐2, 3‐dicarboxylic acid) were synthesized and structurally determined. Complexes 1 and 2 are tetranuclear [Zn^II₂M^II₂] (M = Ni ( 1 ), Cu ( 2 ), respectively) molecules including both oxamide and pzdc^2– bridges. The structure of compound 3 consists of pyrazine‐2, 3‐dicarboxylate and oxamido‐bridged, and is arranged in different butterfly‐like octanuclear molecules. The magnetic susceptibility data of 3 were analyzed.     

Mixed‐Ligand Complexes of Copper(II) with α‐Hydroxycarboxylic Acids and 1,10‐Phenanthroline

Eight new two‐ligand complexes of copper(II) with 1,10‐phenanthroline and one of four different α‐hydroxy‐carboxylic acids (glycolic, lactic, mandelic and benzylic) were prepared. The complexes of general formula [Cu(HL)₂(phen)] · nH₂O (HL = monodeprotonated acid) ( 1 – 4 ) were characterized by elemental analysis, IR, electronic and EPR spectroscopy, magnetic measurements and thermo‐gravimetric analysis. The complexes of general formulae [Cu(HL)(phen)₂](HL) · H₂L · nSolv [ 1 a (HL = HGLYO^–, n = 1, Solv = MeCN) and 3 a (HL = HMANO^–, n = 0)] and [Cu(L)(phen)(OH₂)] · nH₂O [ 2 a (L = LACO^2–, n = 4) and 4 a (L = BENO^2–, n = 2)] were characterized by X‐ray diffractometry. In all these latter a pentacoordinated copper atom has a basically square pyramidal coordination polyhedron, the distortion of which towards a trigonal bipyramidal configuration has been evaluated in terms of the parameter τ. In 1 a and 3 a there are three forms of α‐hydroxycarboxylic acid: a monodentate monoanion, a monoanionic counterion, and a neutral molecule lying in the outer coordination sphere; in 2 a and 4 a the α‐hydroxycarboxylic acid is a bidentate dianion coordinating through carboxyl and hydroxyl oxygens.     

Hydrothermal Synthesis,Crystal Structures and Effect of Non Bonding Interactions in Crystal Packing of Two Mixed‐Ligand Metal Complexes with Glycolato and 2,2′‐Dipiridylamine and with Benzilato and Imidazole

Two new mixed‐ligand complexes [Fe(HG)₂(dipyam)] ( 1 ) (HG = glycolato and dipyam = 2,2′‐dipyridylamine) and [Cu(HB)₂(im)₂]·2H₂O ( 2 ) (HB = benzilato and im = imidazole) have been hydrothermally synthesized and structurally characterised by X‐ray diffraction. In both cases the metallic centre is in an octahedral environment, strongly distorted in 2 (4+2 coordination). The α‐hydroxycarboxylato ligands (glycolato or benzilato) present different coordinative behaviour, bidentade chelate through the hydroxyl oxygen and one carboxy oxygen in 1 and through the two oxygen atoms of the carboxylate group in 2 . The complexes are extended into 2D frameworks through hydrogen bonding and π···π or C‐H···π interactions. The complexes were also characterized by elemental analysis, FT‐IR and UV‐vis spectroscopy and room temperature magnetic measurements.     

Formation of Stable Rhodium η6‐Arene Complexes with Aniline Derivatives

Three new, hitherto unknown, rhodium complexes with aniline and two of its derivatives (2, 6‐dimethylaniline and N‐methylaniline) are presented. All complexes have been characterized by X‐ray analysis.     

Syntheses,Characterization and X‐Ray Structures of the first Copper(I) and Silver(I) Complexes with ATT (ATT = 6‐Aza‐2‐thiothymine)

The reaction of copper(I) chloride with 6‐aza‐2‐thiothymine (ATT, 1 ) and triphenylphosphane in methanol/chloroform gives [(ATT)CuCl(PPh₃)] ( 2 ) as a neutral complex. [(ATT)Ag(NO₃)(PPh₃)₂]·MeOH ( 3 ) can be obtained by the reaction of 1 with silver(I) nitrate and triphenylphosphane in methanol/chloroform in excellent yields and the single crystals of 3 can be obtained from acetonitril solution. Both complexes were characterized by infrared spectroscopy, elemental analyses as well as by X‐ray diffraction studies. Crystal data for 2 at —80 °C: space group I2/a with a = 1859.3(1), b = 1143.2(1), c = 2208.2(1) pm, β = 104.84(1)°, Z = 8, R₁ = 0.0355 and for 3 at —80 °C: space group P2₁/c with a = 1344.1(1), b = 1553.6(1), c = 1977, 3(3) pm, β = 105.26(1)°, Z = 4, R₁ = 0.0436.     

A Robust 3D Cage‐like Ultramicroporous Network Structure with High Gas‐Uptake Capacity

A three‐dimensional (3D) cage‐like organic network (3D‐CON) structure synthesized by the straightforward condensation of building blocks designed with gas adsorption properties is presented. The 3D‐CON can be prepared using an easy but powerful route, which is essential for commercial scale‐up. The resulting fused aromatic 3D‐CON exhibited a high Brunauer–Emmett–Teller (BET) specific surface area of up to 2247 m² g^?1. More importantly, the 3D‐CON displayed outstanding low pressure hydrogen (H₂, 2.64 wt %, 1.0 bar and 77 K), methane (CH₄, 2.4 wt %, 1.0 bar and 273 K), and carbon dioxide (CO₂, 26.7 wt %, 1.0 bar and 273 K) uptake with a high isosteric heat of adsorption (H₂, 8.10 kJ mol^?1; CH₄, 18.72 kJ mol^?1; CO₂, 31.87 kJ mol^?1). These values are among the best reported for organic networks with high thermal stability (ca. 600 °C).